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Leading world powers agreed to slap fresh sanctions on Moscow over the Ukraine crisis as soon as Monday, as tensions mounted amid fears of an imminent Russian invasion.

As the West sought to ratchet up the diplomatic and economic pressure on the Kremlin, the situation on the ground in eastern Ukraine threatened to escalate, with pro-Russian rebels kidnapping an international team of OSCE observers and accusing them of being NATO spies.

The OSCE observers were sent to Ukraine to monitor an April 17 accord signed in Geneva between Russia, Ukraine, the United States and the European Union that was meant to de-escalate the crisis in the ex-Soviet republic.

An EU diplomat said a list adding 15 people to the 55 Russians and Ukrainians already blacklisted by the EU had already been approved in principle.

The crisis erupted after Russia refused to accept the legitimacy of Kiev's new pro-EU government, which came to power after four months of street protests forced the ouster of the Kremlin-backed president, Viktor Yanukovych.

While Obama has ruled out sending US or NATO forces into Ukraine, Washington has begun deploying 600 US troops to bolster NATO's defences in nearby eastern European states.

After meeting Pope Francis, Yatsenyuk, who warned Friday Moscow was trying to trigger a "third world war", asked Russia to pull back its troops.